CN107459594B - Supported iron catalyst, preparation method thereof and iron catalyst system - Google Patents
Supported iron catalyst, preparation method thereof and iron catalyst system Download PDFInfo
- Publication number
- CN107459594B CN107459594B CN201610393136.2A CN201610393136A CN107459594B CN 107459594 B CN107459594 B CN 107459594B CN 201610393136 A CN201610393136 A CN 201610393136A CN 107459594 B CN107459594 B CN 107459594B
- Authority
- CN
- China
- Prior art keywords
- complex
- iron catalyst
- iron
- solvent
- silica gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the field of olefin polymerization catalysts, and particularly provides a supported iron catalyst, a preparation method thereof and an iron catalyst system. The supported iron catalyst comprises a manganese chloride/silica gel carrier and an iron single active center component loaded on the carrier; wherein the precursor of the iron single active center component is a pyridine diimine Fe (II) complex with a structure shown in formula 1, wherein R is1～R10Same or different, each selected from H, halogen or C1～C4When the supported iron catalyst is used for olefin polymerization, compared with a pyridine diimine Fe (II) catalyst which is not modified by manganese chloride, the supported iron catalyst has higher polymerization activity and can ensure that the performance of a polymer is basically unchanged.
Description
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a supported iron catalyst and a preparation method thereof, and an iron catalyst system for olefin polymerization.
Background
During the development of olefin polymerization catalysts, the single-site catalysts developed in the 90 s of the 20 th century have received great development and attention. Particularly, the iron and cobalt metal complex containing the pyridine diimine ligand has high catalytic olefin oligomerization and polymerization activity, can obtain polyolefin resin with the characteristics of functionalization and the like, and has good application prospect. However, when such catalysts are unsupported, the resulting polymers are amorphous and cannot be used in widely used slurry or gas phase polymerization processes.
At present, there are many reports on the single-site catalyst loading research, among which the research on silica gel as a carrier is the most reported (CN1174848A, CN1174849A, CN1356343A, US4,808,561, US5,026,797, US5,763,543, US5,661,098), and such supported catalysts can be used in partial polymerization processes, but the use conditions are harsh, and usually require expensive Methylaluminoxane (MAO) as a cocatalyst, which makes the olefin polymerization cost higher.
There are also references to the use of alkylaluminums and manganese dichloride as additives directly for solution polymerization reactions in boride systems. Compared with the catalyst without adding manganese dichloride, the polymerization activity of the catalyst modified by manganese dichloride is obviously improved, however, the molecular weight and the distribution of the polymer are obviously changed, and the processing performance of the polymer cannot be effectively controlled (US 20010006931).
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a supported iron catalyst, a preparation method thereof, and an iron catalyst system for olefin polymerization.
In the research, the inventor of the present invention found that, when the supported iron catalyst prepared by introducing manganese dichloride (i.e., manganese chloride) into a silica gel carrier and using an iron complex containing a pyridine diimine ligand as a precursor is used for ethylene polymerization, the activity of the catalytic reaction can be significantly improved, and the properties of the polymer obtained by the original iron catalyst (without adding manganese dichloride) are maintained, i.e., the molecular weight and the molecular weight distribution of the polymer are basically unchanged. The present invention has been made based on the above findings.
According to a first aspect of the present invention, there is provided a supported iron catalyst comprising a manganese chloride/silica gel support and an iron single site component supported on the support; wherein the precursor of the iron single active center component is a pyridine diimine Fe (II) complex with a structure shown in a formula 1:
wherein R is1～R10Same or different, each selected from H, halogen or C1～C4Linear or branched alkyl.
According to a second aspect of the present invention, there is provided a process for preparing the supported iron catalyst, the process comprising:
(1) preparation of manganese chloride/silica gel Carrier
In the presence of a first solvent, contacting silica gel with manganese chloride to obtain a mixed solution; then, removing the first solvent in the mixed solution to prepare the manganese chloride/silica gel carrier;
(2) load(s)
Reacting the manganese chloride/silica gel support with the precursor of the iron single site component in the presence of a second solvent.
According to a third aspect of the present invention, there is provided an iron catalyst system for olefin polymerization, the iron catalyst system comprising: the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is the supported iron catalyst.
The supported iron catalyst has good particle shape, and has higher polymerization activity and basically unchanged polymer performance when being used for olefin polymerization. In addition, the iron catalyst system of the invention has wide applicability, can preferably use alkyl aluminum as a cocatalyst, and has the characteristic of low cost compared with the methylaluminoxane which is usually used for olefin polymerization.
Drawings
Fig. 1 a-1 b are SEM images of supported iron catalysts prepared in example 1 of the present invention at different magnifications.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a supported iron catalyst comprising a manganese chloride/silica gel support and an iron single site component supported on the support; wherein the precursor of the iron single active center component is a pyridine diimine Fe (II) complex with a structure shown in a formula 1:
wherein R is1～R10Same or different, each selected from H, halogen or C1～C4Linear or branched alkyl.
According to the invention, the halogen may be selected from Cl, Br or F.
Said C is1～C4Specific examples of the linear or branched alkyl group of (1) include: methyl (Me), ethyl (Et), n-propyl, isopropyl (iPr), n-butyl, isobutyl and tert-butyl, preferably methyl, ethyl and isopropyl.
Preferably, in formula 1, R1、R3、R4And R6Same as R2And R5Same as R7～R10The same is true. In one embodiment, R7～R10Are all H.
More preferably, the precursor of the iron single site component is selected from at least one of the following complexes:
the complex 1: r1＝R3＝R4＝R6＝Me，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
And (2) the complex: r1＝R3＝R4＝R6＝Et，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
And (3) complex: r1＝R3＝R4＝R6＝iPr，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
The complex 4: r1＝R2＝R3＝R4＝R5＝R6＝Me，R7＝R8＝R9＝R10＝H；
And (3) a complex 5: r1＝R3＝R4＝R6＝Me，R2＝R5＝Br，R7＝R8＝R9＝R10＝H；
The complex 6: r1＝R3＝R4＝R6＝Me，R2＝R5＝Et，R7＝R8＝R9＝R10＝H；
The complex 7: r1＝R3＝R4＝R6＝Et，R2＝R5＝Me，R7＝R8＝R9＝R10＝H；
The complex 8: r1＝R3＝R4＝R6＝Et，R2＝R5＝Br，R7＝R8＝R9＝R10＝H；
The complex 9: r1＝R3＝R4＝R6＝F，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
The complex 10: r1＝R3＝R4＝R6＝Cl，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
The complex 11: r1＝R3＝R4＝R6＝Br，R2＝R5＝H，R7＝R8＝R9＝R10＝H。
The pyridine diimine Fe (II) complex can be obtained commercially or prepared according to conventional methods in the field, and specifically, the pyridine diimine Fe (II) complex can be found in J.Am.chem.Soc.1998,120,4049-4050 and WO9902472A1, which are not described herein again.
According to the present invention, the content of Mn may be 0.5 to 7.0 wt% and the content of Fe may be 0.01 to 5 wt% based on the total weight of the supported iron catalyst.
Preferably, based on the total weight of the supported iron catalyst, the content of Mn is 0.5-4.0 wt%, and the content of Fe is 0.2-0.5 wt%; more preferably, the Mn content is 0.5 to 2.5 wt%.
In the invention, the manganese chloride/silica gel carrier is a silica gel carrier modified by manganese chloride, and the size of the supported iron catalyst can be regulated and controlled by the carrier.
According to a second aspect of the present invention, there is provided a process for preparing the supported iron catalyst, the process comprising:
(1) preparation of manganese chloride/silica gel Carrier
In the presence of a first solvent, contacting silica gel with manganese chloride to obtain a mixed solution; then, removing the first solvent in the mixed solution to prepare the manganese chloride/silica gel carrier;
(2) load(s)
Reacting the manganese chloride/silica gel support with the precursor of the iron single site component in the presence of a second solvent.
In the step (1), the first solvent may be a conventional choice in the field of modified silica gel carriers, as long as the silica gel and manganese chloride can be dissolved. For example, the first solvent may be selected from at least one of tetrahydrofuran, ethanol, methanol, propanol, butanol, 2-ethylhexanol, ethylene glycol, and glycerol. Preferably, the first solvent is tetrahydrofuran.
The contacting is typically performed under an inert gas (e.g., nitrogen) blanket, and may include: dissolving manganese chloride in a first solvent, adding silica gel at the temperature of 50-80 ℃, and stirring and dissolving for 0.5-3 hours.
Specific procedures for removing the first solvent may include: firstly, the solvent is evaporated by heating; and then heating and vacuumizing to obtain the manganese chloride/silica gel carrier in a solid powder state. Among them, in order to further obtain a carrier having good fluidity, it is preferable that the heating and the evacuation be performed in two stages, and the conditions of the first stage include: the temperature is 80-150 ℃, and the time is 0.5-3 h; the conditions of the second stage include: the temperature is 200-400 ℃, and the time is 6-15 hours. In addition, whether the first solvent is removed or not can be analyzed by gas chromatography.
In the step (2), the reaction is usually carried out under the protection of an inert gas (e.g., nitrogen), and the specific conditions of the reaction can be carried out with reference to a conventional method of supporting a catalyst. The conditions of the reaction may include: the temperature is 0-80 ℃, preferably 15-40 ℃; the time is 1 to 8 hours, preferably 3 to 6 hours.
The second solvent may be selected from at least one of toluene, benzene, xylene, hexane, heptane, and cyclohexane, and is preferably toluene.
In addition, after the reaction is finished, the method may further include: washing the slurry obtained by the reaction by using a second solvent, and then carrying out vacuum drying to obtain the solid supported iron catalyst.
In the present invention, the amounts of the first solvent and the second solvent may be selected according to the prior art, and are not described herein again.
The supported iron catalysts can be used directly for the polymerization of olefins, for example in gas-phase polymerization processes, or else with addition of cocatalysts (e.g.MAO, aluminum alkyls).
According to a third aspect of the present invention, there is provided an iron catalyst system for olefin polymerization, the iron catalyst system comprising: the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is the supported iron catalyst.
The cocatalyst is preferably an aluminum alkyl. In the invention, the impurities in the polymerization system can be removed by adding the alkyl aluminum in the polymerization reaction, and the polymerization activity is improved to a certain extent without adding expensive MAO as a cocatalyst.
Preferably, the alkyl aluminum is selected from at least one of trimethyl aluminum, triethyl aluminum (TEA), tripropyl aluminum, tributyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-tert-butyl aluminum, tripentylaluminum, trihexyl aluminum, trioctylaluminum, diethyl aluminum monochloride and ethyl aluminum dichloride.
In the case of an aluminum alkyl co-catalyst, the molar ratio of Fe/Al in the catalyst system may be 1: 1.0X 104～1.0×105。
The iron catalyst system can be used in different polymerization processes, such as gas phase polymerization, slurry polymerization, and the like, can be used for homopolymerization or copolymerization of olefins, and is particularly suitable for homopolymerization of ethylene or copolymerization of ethylene with other α -olefins, wherein non-limiting examples of α -olefins can include propylene, butene, pentene, hexene, octene, 4-methylpentene-1, and the like.
The solvent used for the polymerization may be selected from alkanes, aromatic hydrocarbons or halogenated hydrocarbons, preferably one or a mixture of hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform and dichloroethane, more preferably hexane.
The concentration of the supported iron catalyst during polymerization can be 1 x 10 in terms of Fe element-8mol/L～1×10- 2mol/L。
The polymerization temperature can be 0-80 ℃; the polymerization pressure may be 1 to 40 MPa.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, a silica gel type 2485 available from Ragedes-Davis company was used, and various solvents were dried before use.
The weight percentage of the metal in the supported iron catalyst is determined by the following method: adopts plasma emission spectrometry (ICP), and adopts a P1000 type ICP-AES plasma emission spectrometer produced by PE company in America.
The polymer molecular weight and molecular weight distribution were determined by the following methods: gel Permeation Chromatography (GPC) is adopted, a Waters Alliance GPCV 2000 is adopted as an instrument, the solvent is 1,2, 4-trichlorobenzene, the sample concentration is 1mg/mL, and the solvent flow rate is 1.0 mL/min; the measurement temperature was 150 ℃.
Example 1
This example illustrates the supported iron catalyst and the method of preparation of the present invention.
1) Preparation of manganese chloride/silica gel carrier
Under the protection of nitrogen, 0.55 g of manganese chloride is added into a glass reactor at room temperature, then 500 ml of tetrahydrofuran is added, stirring is started, 8.6 g of silica gel is added into the reactor, the temperature is raised to 65 ℃, the mixture is stirred and dissolved for 2 hours, and then the solvent is evaporated at 80 ℃ to obtain white solid powder. And (3) drying the white solid powder at 100 ℃ for 2 hours in vacuum, and then drying at 300 ℃ for 10 hours in vacuum to obtain a solid manganese chloride/silica gel carrier with good fluidity, wherein the tetrahydrofuran cannot be detected through gas chromatography analysis.
2) Loading of iron single site catalysts
Under the protection of nitrogen, 0.9 g of the prepared manganese chloride/silica gel carrier is added into a glass reactor, 20 ml of toluene is added to prepare slurry, 0.036g of Fe catalyst precursor 2, 6-bis [1- (2,4, 6-trimethylbenzene imine) methyl ] pyridine iron dichloride (namely, complex 4) is added into the reactor, the reaction is carried out for 4 hours at 25 ℃, then 15 ml of toluene is used for washing, and vacuum drying is carried out, so as to obtain the supported iron catalyst A product. The microscopic morphology of the supported iron catalyst is shown in fig. 1a and fig. 1b, and the particle morphology of the catalyst is good as can be seen from the figure. In addition, the contents of metals in the product are shown in table 1.
Example 2
This example illustrates the supported iron catalyst and the method of preparation of the present invention.
1) Preparation of manganese chloride/silica gel carrier
Under the protection of nitrogen, 0.95 g of manganese chloride is added into a glass reactor at room temperature, then 500 ml of tetrahydrofuran is added, stirring is started, 10.4 g of silica gel is added into the reactor, the temperature is raised to 65 ℃, the mixture is stirred and dissolved for 2 hours, and then the solvent is evaporated at 80 ℃ to obtain white solid powder. And (3) drying the white solid powder at 100 ℃ for 2 hours in vacuum, and then drying at 300 ℃ for 10 hours in vacuum to obtain a solid manganese chloride/silica gel carrier with good fluidity, wherein the tetrahydrofuran cannot be detected through gas chromatography analysis.
2) Loading of iron single site catalysts
Under the protection of nitrogen, 1.0 g of the prepared manganese chloride/silica gel carrier is added into a glass reactor, 20 ml of toluene is added to prepare slurry, 0.041g of Fe catalyst precursor 2, 6-bis [1- (2,4, 6-trimethylbenzene imine) methyl ] pyridine iron dichloride is added into the reactor to react for 4 hours at 25 ℃, and then the supported iron catalyst B product is obtained by washing with 15 ml of toluene and vacuum drying. The metal content of this product is shown in table 1.
Example 3
This example illustrates the supported iron catalyst and the method of preparation of the present invention.
1) Preparation of manganese chloride/silica gel carrier
Under the protection of nitrogen, 1.11 g of manganese chloride is added into a glass reactor at room temperature, then 500 ml of tetrahydrofuran is added, after stirring, 10.8 g of silica gel is added into the reactor, the temperature is raised to 65 ℃, the mixture is stirred and dissolved for 2 hours, and then the solvent is evaporated at 80 ℃ to obtain white solid powder. And (3) drying the white solid powder at 100 ℃ for 2 hours in vacuum, and then drying at 300 ℃ for 10 hours in vacuum to obtain a solid manganese chloride/silica gel carrier with good fluidity, wherein the tetrahydrofuran cannot be detected through gas chromatography analysis.
2) Loading of iron single site catalysts
Under the protection of nitrogen, 0.8 g of the prepared manganese chloride/silica gel carrier is added into a glass reactor, 20 ml of toluene is added to prepare slurry, 0.031g of Fe catalyst precursor 2, 6-bis [1- (2,4, 6-trimethylbenzene imine) methyl ] pyridine iron dichloride is added into the reactor to react for 4 hours at 25 ℃, and then the reaction product is washed by 15 ml of toluene and dried in vacuum, so as to obtain a load type iron catalyst C product. The metal content of this product is shown in table 1.
Comparative example 1
Under the protection of nitrogen, 1.0 g of silica gel carrier is added into a glass reactor, 20 ml of toluene is added to prepare slurry, 0.037g of Fe catalyst precursor 2, 6-bis [1- (2,4, 6-trimethylbenzene imine) methyl ] pyridine iron dichloride is added into the reactor to react for 4 hours at 25 ℃, and then the supported Fe catalyst D1 product is obtained after washing by 15 ml of toluene and vacuum drying. The metal content of this product is shown in table 1.
Test examples 1 to 4
High pressure ethylene polymerization experiment
In a 1-liter stainless steel high-pressure polymerizer, nitrogen and ethylene were each replaced three times, and then 500 ml of a hexane solvent and 1 ml of a1 mol/l hexane solution of Triethylaluminum (TEA) were added, followed by addition of 120 mg of the supported catalysts A to C and D prepared in the above examples and comparative examples, respectively, heating to 30 ℃ and raising the pressure to 10MPa, and reacting under the pressure for 1 hour. After the polymerization reaction is finished, cooling, collecting polyethylene particle powder, and weighing. The polymerization activity and polymer properties in this experiment are shown in table 2.
TABLE 1
| Numbering | Supported iron catalyst | Mn content/% wt | Fe content/% wt |
| Example 1 | A | 1.97 | 0.31 |
| Example 2 | B | 2.08 | 0.32 |
| Example 3 | C | 2.24 | 0.33 |
| Comparative example 1 | D1 | - | 0.30 |
TABLE 2
As a result of comparing the results of examples 1 to 3 with that of comparative example 1, MnCl was found2The addition of (A) can improve the polymerization activity of the iron catalyst and also can basically ensure the molecular weight and the distribution of the polymer.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A method for preparing a supported iron catalyst, the supported iron catalyst comprising a manganese chloride/silica gel carrier and an iron single active center component supported on the carrier; wherein the precursor of the iron single active center component is a pyridine diimine Fe (II) complex with a structure shown in a formula 1:
wherein R is1～R10Same or different, each selected from H, halogen or C1～C4Linear or branched alkyl of (a);
the method is characterized by comprising the following steps:
(1) preparation of manganese chloride/silica gel Carrier
In the presence of a first solvent, contacting silica gel with manganese chloride to obtain a mixed solution; then, removing the first solvent in the mixed solution to prepare the manganese chloride/silica gel carrier;
(2) load(s)
Reacting the manganese chloride/silica gel support with the precursor of the iron single site component in the presence of a second solvent.
2. The method according to claim 1, wherein in formula 1, R1、R3、R4And R6Same as R2And R5Same as R7～R10The same is true.
3. The method of claim 1, wherein the precursor of the iron single site component is selected from at least one of the following complexes:
the complex 1: r1＝R3＝R4＝R6＝Me，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
And (2) the complex: r1＝R3＝R4＝R6＝Et，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
And (3) complex: r1＝R3＝R4＝R6＝iPr，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
The complex 4: r1＝R2＝R3＝R4＝R5＝R6＝Me，R7＝R8＝R9＝R10＝H；
And (3) a complex 5: r1＝R3＝R4＝R6＝Me，R2＝R5＝Br，R7＝R8＝R9＝R10＝H；
The complex 6: r1＝R3＝R4＝R6＝Me，R2＝R5＝Et，R7＝R8＝R9＝R10＝H；
The complex 7: r1＝R3＝R4＝R6＝Et，R2＝R5＝Me，R7＝R8＝R9＝R10＝H；
The complex 8: r1＝R3＝R4＝R6＝Et，R2＝R5＝Br，R7＝R8＝R9＝R10＝H；
The complex 9: r1＝R3＝R4＝R6＝F，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
The complex 10: r1＝R3＝R4＝R6＝Cl，R2＝R5＝H，R7＝R8＝R9＝R10＝H；
The complex 11: r1＝R3＝R4＝R6＝Br，R2＝R5＝H，R7＝R8＝R9＝R10＝H。
4. The method according to any one of claims 1 to 3, wherein the Mn content is 0.5 to 7.0 wt% and the Fe content is 0.01 to 5 wt%, based on the total weight of the supported iron catalyst.
5. The method according to claim 1, wherein, in the step (1), the first solvent is at least one selected from the group consisting of tetrahydrofuran, ethanol, methanol, propanol, butanol, 2-ethylhexanol, ethylene glycol and glycerol;
in the step (2), the second solvent is at least one selected from the group consisting of toluene, benzene, xylene, hexane, heptane and cyclohexane.
6. The method of claim 5, wherein the first solvent is tetrahydrofuran.
7. The method of claim 5, wherein the second solvent is toluene.
8. The method of claim 1, wherein in step (2), the reaction conditions comprise: the temperature is 0-80 ℃ and the time is 1-8 hours.
9. An iron catalyst system for olefin polymerization, the iron catalyst system comprising: a main catalyst and a cocatalyst, wherein the main catalyst is a supported iron catalyst prepared by the method of any one of claims 1-8.
10. The iron catalyst system of claim 9, wherein the co-catalyst is an aluminum alkyl.
11. The iron catalyst system of claim 10, wherein the alkyl aluminum is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum monochloride, and ethylaluminum dichloride.
12. The iron catalyst system of claim 11, wherein the tripropylaluminum is triisopropylaluminum; the tributyl aluminum is triisobutyl aluminum and/or tri-tert-butyl aluminum.
13. The iron catalyst system of claim 10, wherein the molar ratio of Fe/Al is 1: 1.0X 104～1.0×105。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610393136.2A CN107459594B (en) | 2016-06-06 | 2016-06-06 | Supported iron catalyst, preparation method thereof and iron catalyst system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610393136.2A CN107459594B (en) | 2016-06-06 | 2016-06-06 | Supported iron catalyst, preparation method thereof and iron catalyst system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107459594A CN107459594A (en) | 2017-12-12 |
| CN107459594B true CN107459594B (en) | 2020-02-18 |
Family
ID=60544889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610393136.2A Active CN107459594B (en) | 2016-06-06 | 2016-06-06 | Supported iron catalyst, preparation method thereof and iron catalyst system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107459594B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656581B (en) * | 2022-03-28 | 2022-12-06 | 安徽泽升科技有限公司 | Preparation method of pyridine diimine iron catalyst regulated and controlled by electronic effect |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302820A (en) * | 1999-12-27 | 2001-07-11 | 住友化学工业株式会社 | Modified particles and preparation method of olefine polymerization catalyst and olefine polymer using said particle |
| CN103374084A (en) * | 2012-04-13 | 2013-10-30 | 中国石油天然气股份有限公司 | Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054137C (en) * | 1997-07-18 | 2000-07-05 | 中山大学 | Ethylene gaseous phase polymerization multifunction catalyst and its preparation method |
| US7541413B2 (en) * | 2007-10-02 | 2009-06-02 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalysts, their synthesis and use |
-
2016
- 2016-06-06 CN CN201610393136.2A patent/CN107459594B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302820A (en) * | 1999-12-27 | 2001-07-11 | 住友化学工业株式会社 | Modified particles and preparation method of olefine polymerization catalyst and olefine polymer using said particle |
| CN103374084A (en) * | 2012-04-13 | 2013-10-30 | 中国石油天然气股份有限公司 | Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107459594A (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101189270B (en) | Process for the polymerization of olefins | |
| Severn et al. | MgCl2-based supports for the immobilization and activation of nickel diimine catalysts for polymerization of ethylene | |
| JP2009507124A (en) | Olefin polymerization catalyst system | |
| KR20140138966A (en) | Method for producing olefin polymer | |
| EP3246343A1 (en) | Method for preparing polyolefin | |
| CN116710496A (en) | Olefin-based polymer and process for producing the same | |
| JP2004509129A (en) | Use of CR Complex for Polymerization of CR Complex and α-Olefin | |
| CN107459594B (en) | Supported iron catalyst, preparation method thereof and iron catalyst system | |
| EP3318544B1 (en) | Process for the preparation of polymerized polyethylene wax | |
| CN107459592B (en) | Modified silica gel carrier, supported metallocene catalyst, preparation method and metallocene catalyst system | |
| CN107459597B (en) | Supported iron catalyst, preparation method thereof and iron catalyst system | |
| WO2005061109A1 (en) | A catalyst system for ethylene (co)-polymerization | |
| CN107663248B (en) | Catalyst composition for long-chain alpha-olefin polymerization and method for catalyzing long-chain alpha-olefin polymerization by using catalyst composition | |
| Gagieva et al. | Ethylene polymerization using immobilized fluorine-containing bis-salicylidenimine-titanium complexes | |
| CN112552429B (en) | Supported metallocene catalyst and preparation method and application thereof | |
| JP7313344B2 (en) | Heterogeneous pre-catalyst for the preparation of highly crystalline, non-entangled ultra-high molecular weight polyethylene (UHMWPE) and its preparation method | |
| CN1414982A (en) | Active, heterogeneous supported bi-or tri-dentate olefin polymerisation catalyst | |
| CN111116810B (en) | Preparation method of olefin-olefin alcohol copolymer | |
| KR20010024474A (en) | Reduced oxidation state transition metal compounds useful as olefin polymerization catalysts | |
| CN114478868B (en) | Late transition metal catalyst for olefin polymerization and preparation method and application thereof | |
| US20030060585A1 (en) | Process for polymerizing alpha-olefins | |
| CN114478866B (en) | Catalyst for olefin polymerization, preparation method and application thereof | |
| CN110964138B (en) | Magnesium single-carrier segmented in-situ supported non-metallocene catalyst and preparation method thereof | |
| CN110964136B (en) | Composite carrier supported non-metallocene catalyst, preparation method and application thereof | |
| CN109485762B (en) | Supported non-metallocene catalyst, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |